阅读说明：本技术 一种酮醛树脂基反应型阴离子乳化剂及其制备方法 (Ketone-aldehyde resin-based reactive anionic emulsifier and preparation method thereof ) 是由 张延武 赵欢欢 李超峰 姜俊青 于 2020-05-06 设计创作，主要内容包括：本发明公开了一种酮醛树脂基反应型阴离子乳化剂及其制备方法,属于高分子技术领域,其制备方法包括以下步骤：将酮醛树脂与顺丁烯二酸酐混合均匀,加热到30-120℃恒温反应5-15h,反应结束后再加入氢氧化钠等溶液进行碱中和,可以得到两亲性高分子乳化剂。本发明得到的树脂成本较低,工艺简便,操作简单,原料可回收利用,较好的两亲性,链端含有双键,HLB值为8-18,软化点在30-80℃。制备环己烷、苯乙烯、甲基丙烯酸甲酯、醋酸乙烯酯类单体的水乳液,乳液的平均粒径为0.1-15μm,具有机械稳定性、低温稳定性以及静置稳定性。(The invention discloses a ketonic aldehyde resin based reactive anionic emulsifier and a preparation method thereof, belonging to the technical field of macromolecules, wherein the preparation method comprises the following steps of uniformly mixing ketonic aldehyde resin and maleic anhydride, heating to 30-120 ℃ for constant-temperature reaction for 5-15H, adding sodium hydroxide and other solutions after the reaction is finished for alkali neutralization to obtain an amphiphilic polymer emulsifier.)

1. A preparation method of a ketone-aldehyde resin-based reactive anionic emulsifier is characterized by comprising the following steps:

(1) adding the ketone-aldehyde resin and maleic anhydride into a reaction kettle, uniformly mixing, and stirring at a constant temperature to react to obtain double-bond end-capped ketone-aldehyde resin; the hydroxyl value range of the ketone-aldehyde resin is 2mmol/g-8mmol/g, the viscosity range is 0.3Pa.s-5Pa.s, the ketone-aldehyde resin is liquid or solid, and the ketone monomer in the ketone-aldehyde resin is one or two of acetone, cyclohexanone and acetophenone; the aldehyde monomer is one or two of formaldehyde and isobutyraldehyde; the molar ratio of hydroxyl in the ketone-aldehyde resin to maleic anhydride is 1: 0.5-10;

(2) neutralizing the obtained double-bond end-capped ketone-aldehyde resin with alkali liquor, and drying to obtain the amphiphilic polymer emulsifier.

2. The method for preparing the ketone-aldehyde resin based reactive anionic emulsifier according to claim 1, wherein the isothermal temperature in step (1) is any one of 30-120 ℃ and the isothermal reaction time is 5-15 hours.

3. The method for preparing the ketone-aldehyde resin-based reactive anionic emulsifier according to claim 1, wherein in the step (2), the alkali solution is sodium hydroxide solution, potassium hydroxide solution, triethanolamine solution, ethylenediamine solution, etc., and the amount of the alkali solution added is 0.5-2 times of the molar amount of the hydroxyl groups in the ketone-aldehyde resin.

4. A ketone-aldehyde resin-based reactive anionic emulsifier obtainable by the process according to any one of claims 1 to 3.

5. The ketoaldehyde resin based reactive anionic emulsifier according to claim 4, characterized in that the chain end contains a reactive double bond, the emulsifier H L B has a value of 8-18 and the softening point of the emulsifier is 30-80 ℃.

Technical Field

The invention belongs to the field of macromolecules, and particularly relates to a ketone-aldehyde resin-based reactive anionic emulsifier and a preparation method thereof.

Background

Emulsifiers, also known as surfactants, are substances that reduce the surface tension of two phases during the preparation of an emulsion, so that the emulsion forms a homogeneous and stable system, and because emulsions are thermodynamically unstable systems, micelles can only be formed if the surface tension is adjusted by adding emulsifiers, so that the oil phase or the aqueous phase can better and more stably exist in the other phase. The choice of emulsifier therefore plays a crucial role in the properties of the emulsion.

According to the size of molecular weight, the emulsifier can be divided into a low molecular emulsifier, a middle molecular emulsifier and a high molecular emulsifier, wherein the common low molecular emulsifier and the middle molecular emulsifier combine an oil phase and a water phase together through weak intermolecular van der Waals force, and because the intermolecular acting force is weak, the emulsion can form two-phase separation in the preparation or storage process, particularly, when the coating is formed into a film, the emulsion prepared by the middle-low molecular emulsifier can be gathered on the surface of the film, thereby greatly influencing the appearance and the performance of the coating film. The polymer chain on the high molecular emulsifier has a certain steric hindrance effect, the surface tension is reduced to form micelles in the emulsifying process, the stability between phase interfaces can be greatly improved through the steric hindrance effect, the performance is excellent, and the high molecular emulsifier also has lower critical micelle concentration and diffusion coefficient than the common emulsifier, so that the development direction of the emulsifier in the future can be reached.

Ketone-aldehyde resins are low molecular weight linear polymers obtained by the condensation reaction of ketones and their derivatives with aldehydes under the catalytic action of bases. Cyclohexanone, formaldehyde and the like are used as important industrial raw materials, the yield is high, the cost is low, the length of the molecular chain segment of the synthesized resin is controllable, the state can be from solid state to liquid state, the solubility is adjusted from oil dissolution to water dissolution, the segment contains carbonyl and hydroxyl, and the carbonyl and the hydroxyl can be associated to form a hydrogen bond, so that the polarity of the whole molecule can be reduced, the resin has better solubility in water and most organic solvents, but the hydrophilic group of the hydroxyl is weaker, the stability of the water phase and the oil phase is poor, the resin cannot be directly used as an amphiphilic emulsifier, but the hydroxyl enables the ketone-aldehyde resin to have better modification conditions. In order to prepare the reactive polymer emulsifier, the ketonic-aldehyde resin and the maleic anhydride are esterified, carboxyl and double bonds are introduced, and the obtained emulsifier has double functions of reaction and emulsification.

Disclosure of Invention

The invention aims to provide a ketone-aldehyde resin based reactive anionic emulsifier and a preparation method thereof.

Based on the purpose, the invention adopts the following technical scheme:

a preparation method of a ketone-aldehyde resin-based reactive anionic emulsifier comprises the following steps:

(1) adding the ketone-aldehyde resin and maleic anhydride into a reaction kettle, uniformly mixing, stirring at constant temperature, reacting to obtain double-bond end-capped ketone-aldehyde resin (also called as esterification product, the acid value is 1 mmol/g-4 mmol/g, carboxyl is contained in the resin before neutralization without adding alkali, and the acid value of the resin can be obtained by titrating the resin with standard alkali solution); the hydroxyl value range of the ketone-aldehyde resin is 2mmol/g-8mmol/g, the viscosity range is 0.3Pa.s-5Pa.s, the ketone-aldehyde resin is liquid or solid, and the ketone monomer in the ketone-aldehyde resin is one or two of acetone, cyclohexanone and acetophenone; the aldehyde monomer is one or two of formaldehyde and isobutyraldehyde; the molar ratio of hydroxyl in the ketone-aldehyde resin to maleic anhydride is 1: 0.5-10;

(2) neutralizing the obtained double-bond end-capped ketone-aldehyde resin with alkali liquor, and drying to obtain the amphiphilic polymer emulsifier.

Further, the constant temperature in the step (1) is any specific temperature of 30-120 ℃, and the constant temperature reaction time is 5-15 hours.

Further, in the step (2), the alkali liquor is sodium hydroxide solution, potassium hydroxide solution, triethanolamine solution, ethylenediamine solution, etc., and the addition amount of the alkali liquor is 0.5-2 times of the molar amount of the hydroxyl in the ketone-aldehyde resin.

The molecular weight of the aldehyde ketone resin is 800-1500.

The ketone-aldehyde resin-based reactive anionic emulsifier prepared by the preparation method has reactive double bonds at the chain end, the value of H L B of the emulsifier is 8-18, and the softening point of the emulsifier is 30-80 ℃.

The invention takes ketone-aldehyde resin and maleic anhydride as raw materials to react, and then the reaction is neutralized by alkali to form the reactive anionic emulsifier, and the obtained emulsifier has good emulsifying property, simple preparation, simple and convenient operation in the production process, less side reaction, equipment cost saving and production cost saving.

Drawings

FIG. 1 is a photograph showing the appearance of a raw material ketone-aldehyde resin in each example of the present invention;

FIG. 2 is a chart of an infrared spectrum of a raw material ketone-aldehyde resin in each example of the present invention;

FIG. 3 is an infrared spectrum of the esterified product of example 1 of the present invention; a: and (3) esterification product b: a ketone-aldehyde resin;

FIG. 4 is an infrared spectrum of a saponified product of an example of the present invention; a: and (3) esterification product b: potassium hydroxide saponification product c: sodium hydroxide d: triethanolamine;

FIG. 5 is a diagram of the emulsifier product prepared in example 1.

Detailed Description

The technical solution of the present invention is further described in detail with reference to the following specific examples, which should not be construed as limiting the scope of the present invention.

The preparation process of the ketone-aldehyde resin comprises the following specific steps:

the ketone monomer comprises acetone, cyclohexanone, acetophenone and the like; the aldehyde monomer comprises formaldehyde, isobutyraldehyde and the like;

(1) mechanism of synthesis (taking cyclohexanone-formaldehyde as an example)

(2) Preparation method

The ketone monomer, the aldehyde monomer and the solid base catalyst were sequentially added to a 100 ml three-necked flask, a thermometer was inserted below the liquid level, and a serpentine condenser tube was installed. The reaction temperature is 80-100 ℃, the reaction time is 8-16h, and after the reaction is finished, the reaction liquid is centrifugally separated, and the rotating speed is 8000 r/min. Centrifuging, separating into solid phase and liquid phase, performing rotary evaporation on the liquid phase to remove unreacted substances,

and recovering the solid-phase catalyst. Putting the rotary evaporated resin into a vacuum drying oven, and vacuum-drying at 65 ℃ for 12 h to obtain a colorless transparent liquid with the specific appearance shown in figure 1.

In terms of mole ratios, ketone monomer: the aldehyde monomer =1:1-1.6, and the catalyst is 5% -20% of the mass of the ketone monomer.

(3) Specific structure confirmation

The functional groups of the resin were characterized by infrared, and the results are shown in FIG. 2. At 3344 cm^-1The stretching vibration absorption peak of hydroxyl (-OH) appears nearby, and is 1028 cm^-1A stretching vibration absorption peak of a carbon-oxygen bond (C-O) corresponding to a hydroxyl group appears nearby; at 2932 cm^-1An absorption peak of antisymmetric stretching vibration of methylene (CH 2) appears nearby, and the absorption peak is 2865 cm^-1In the vicinity of which methylene (CH) is present₂) Has a peak absorption of 1451 cm^-1In the vicinity of which methylene (CH) is present₂) A bending vibration absorption peak of (1); at 1689 cm^-1An absorption peak of stretching vibration of a carbonyl group (C = O) appears in the vicinity. The above results indicate the successful synthesis of ketone-aldehyde resins.

For detailed preparation, reference may be made to CN2018103743381 [ paragraphs 0057 to 0116 ].

The preparation method of the ketone-aldehyde resin-based reactive anionic emulsifier mainly comprises the following steps: esterification stage, alkali neutralization stage.

Mono, esterification

The molar ratio of hydroxyl and maleic anhydride in the ketone-aldehyde resin is from 1:0.5 to 1:10, the temperature is 30-120 ℃, and the constant temperature reaction is carried out for 5-15 hours.

II, alkali neutralization

Taking a certain amount of double-bond end-capped ketone-aldehyde resin, respectively adding a potassium hydroxide solution, a sodium hydroxide solution, a triethanolamine solution and the like, reacting until the solution is neutral, and drying.

The reaction principle of the ketone-aldehyde resin-based reactive anionic emulsifier is as follows: